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A G2 Study of the Triplet [H

4

,Si,P]

+

Potential Energy Surface.

Mechanism for the Reaction of P

+

₍

3

_{P) with Silane.}

Elso M. Cruz†_{, Xabier Lopez, Martín Sarobe}‡_{, Fernando P. Cossío}

and Jesus M. Ugalde*_.

Kimika Fakultatea, Euskal Herriko Unibertsitatea, P.K. 1072, 20080 Donostia, Euskadi, Spain.

Supplementary Material

†_{On leave from: Dpto de Química, Fac. de Ciencias Nat. y Mat., Universidad de}

Oriente, Avda. Patricio Lumumba s/n, 90500 Santiago de Cuba, Cuba.

‡_{Permanent address: Debye Institute, Department of Physical Organic Chemistry,}

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Table I. Cartesian coordinates (in Å), calculated at the MP2/6-31G(d,p) level of

theory, for the intermediates and transition states of the triplet [H₄,Si,P]+ PES.

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Species Atom x y z

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1 Si -1.265187 -.109568 .000000

P .998549 .018458 .000000

H -1.909007 1.207740 .000004

H 1.541539 -1.261171 .000000

H 1.550925 .655259 1.107716

H 1.550924 .655265 -1.107713

2 P 1.210530 .092491 .000000

Si -1.146004 -.022106 .000000

H 2.114620 -.974128 .000003

H -1.465438 1.401146 -.000002

H -1.381537 -.752449 1.243293

H -1.381537 -.752456 -1.243289

3 P -1.097300 .045340 -.040918

Si 1.209854 -.061666 -.069078

H -1.825039 -1.080923 -.411143

H -1.800833 .662699 .991485

H 1.604856 1.343504 -.187395

H 1.542558 -.742065 1.187915

4 P -1.300954 .040107 .003227

Si .929260 -.194846 -.001317

H 1.654938 -.439082 1.245596

H 1.653650 -.545680 -1.221064

H 1.400993 1.618786 -.344503

H 1.795075 1.492216 .290006

5 Si -1.500821 -.000437 .000088

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Table I. Continued.

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6 P 1.192682 .075102 -.115350

Si -1.018177 -.257794 .103748

H -1.747538 -.395350 -1.168649

H 1.508472 -.255733 1.216454

H -1.623177 1.557560 .486365

H -1.773511 1.576107 -.256390

7 P -1.110426 .022238 -.000012

Si 1.233188 -.409251 -.000107

H -1.931054 .186482 1.115015

H -1.930396 .190513 -1.114922

H 1.626609 2.509585 -.368259

H 1.626598 2.509361 .369835

8 Si .000000 .000000 -1.504122

H .000000 1.142676 -.524635

H .000000 -1.142676 -.524635

P .000000 .000000 1.777974

H 1.239148 .000000 -2.281312

H -1.239148 .000000 -2.281312

TS 2/5 P -1.213717 -.085996 .000137

Si 1.035206 -.075900 .000091

H 1.754510 -.247396 1.263296

H 1.754365 -.252420 -1.262505

H -.434479 1.314040 -.002076

H .638488 1.538327 -.002045

TS 3/7 P -1.184730 .003809 -.099715

Si 1.313734 -.348710 .017826

H -1.873703 -.949695 .659244

H -1.599590 1.167543 .558189

H 1.443223 2.302270 -.355739

H 1.408741 2.304694 .384475

TS 1/Si Si 1.474527 .053190 .000001

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Table I. Continued.

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TS 2/6 P -1.224869 .028690 -.089277

Si 1.003515 -.130640 -.006788

H 2.108965 -1.077750 .007960

H -1.333672 -.077706 1.313479

H 1.786033 1.285647 -.368919

H 1.762502 1.268420 .481663

TS 1/3 Si -1.175803 -.108885 -.002680

P 1.003474 -.000977 .002122

H -1.986518 .979437 -.574106

H .028558 .163220 1.264393

H 1.456080 1.306090 -.122258

H 1.911015 -.909702 -.562330

TS 2/3 P -1.084789 -.017999 .019924

Si 1.093943 -.005365 -.017595

H -2.241095 -.069586 -.823022

H -.319595 .426305 1.273007

H 1.675135 1.251116 -.489466

H 1.842190 -1.262743 -.013048

TS 2/4 P -0.034346 1.398057 .000000

Si -0.034346 -1.237658 .000000

H 1.179057 .623882 .000000

H .655772 -1.508946 1.254146

H .655772 -1.508946 -1.254146

H -1.494556 -1.249634 .000000

TS 2/H P -1.207012 -.040977 -.059437

Si .993042 -.134449 .063482

H 1.755560 -.824773 -.975294

H 1.959406 1.901744 -.889328

H 1.723169 .203934 1.285479

H -1.235545 1.216041 .581955

TS 3/H P 1.044652 -.061411 -.074971

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Table II. Spin density, atomic charges (Q) and dipole moments (debye) at the MP2/6-31G(d,p) // MP2/6-MP2/6-31G(d,p) level of theory for the intermediates of the triplet

[H₄,Si,P]+ PES.

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Species Atoms Spin Q _

Density Mulliken Natural

2 P 2.029 0.327 0.506 0.985

Si 0.777 0.900

H_(P) 0.079 0.016

H_1(Si) -0.062 -0.140

H_2(Si) -0.060 -0.141

H_3(Si) -0.060 -0.141

3 P 1.132 0.333 0.427 1.382

Si 0.925 0.628 0.820

H_1(P) 0.072 0.047

H_2(P) 0.072 0.047

H_1(Si) -0.053 -0.171

H_2(Si) -0.052 -0.170

4 P 1.944 0.209 0.187 3.789

Si 0.696 0.907

H_1(Si) -0.043 -0.138

H_2(Si) -0.028 -0.137

H_3(Si) 0.063 0.071

H_4(Si) 0.102 0.110

5 P 2.062 0.604 0.628 9.707

Si 0.938 1.207

H_(P,Si) -0.395 -0.390

H_1(Si) -0.049 -0.148

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Table II. Continued...

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6 P 1.276 0.223 0.163 3.166

Si 0.739 0.665 0.921

H_(P) 0.013 -0.021

H_1(Si) -0.044 -0.198

H_2(Si) 0.043 0.030

H_3(Si) 0.099 0.102

7 P 1.187 0.238 0.243 1.042

Si 0.911 0.597 0.657

H_1(P) 0.069 0.044

H_2(P) 0.069 0.044

H_1(Si) 0.013 0.005

H_2(Si) 0.013 0.005

8 P 2.010 0.828 0.914 4.609